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Measurements of Activity Coefficients at Infinite Dilution for Organic Solutes and Water in the Ionic Liquid 1-Butyl-1-methylpiperidinium Thiocyanate Urszula Doman´ska*,†,‡ and Marta Kro´likowska† Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland, and Thermodynamic Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4001, South Africa
The activity coefficients at infinite dilution (γ∞13) for 33 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, and water in the ionic liquid, 1-butyl-1methylpiperidinium thiocyanate ([BMPIP][SCN]), were determined by gas-liquid chromatography over the temperature range (318.15 to 358.15) K. The partial molar excess enthalpies at infinite dilution values ∞ (∆HE,∞ 1 ) were calculated from the experimental γ13 values, obtained over the temperature range. The selectivities for heptane/benzene, cyclohexane/benzene, and heptane/thiophene separation problems were calculated from the γ∞13 and compared to the literature values for other ionic liquids with thiocyanate-based anion or with a butyl-methyl-substituted cation.
Introduction Ionic liquids (ILs) have unique properties that make them suitable substitutes for use in technological processes for volatile organic compounds. Recently, the interest of new ILs is increasing to the pyrrolidinium-based ILs1–3 and piperidiniumbased ILs.4–10 The specific properties of piperidinium-based ILs are: a broad temperature range of the liquid phase, extremely low vapor pressure, a structure similarity to pyrrolidinium-based ILs, high solubility in water, low toxicity, and a density lower than those of pyrrolidinium-based ILs. All of these physicochemical properties make the piperidinium-based ILs potentially useful in many industrial processes. The 1-ethylpiperidinium tetrafluoroborate was used in the electrochemical processes.5 A high thermal stability, possible application in lithium-ion batteries and other electrochemical devices, high ionic conductivity, and low toxicity were presented for 1-alkyl-1-methylpiperidinium-based and 1-alkyl-1-methylpyrrolidinium-based ILs with different anions.7 The mutual solubility of 1-propyl-1methylpiperidinium bis{(trifluoromethyl)sulfonyl}imide, [PMPIP][NTf2], with water was measured and calculated with a conductor-like screening model for real solvent (COSMORS) or a quantitative structure-property relationship (QSPR) model.8,9 Densities and isothermal compressibilities of different ILs including the piperidinium-based ILs and pyrrolidiniumbased ILs were measured and discussed for different anions and cations.10 Unfortunately, it was shown that the viscosity for the thiocyanate anion, [SCN]-, is slightly higher than that for the [NTf2]- anion and that the viscosity for the 1-propyl-1-methylpiperidinium cation is higher than for imidazolium-, pyrrolidinium-, and ammonium-based cations.11 The phase equilibrium (liquid + liquid), LLE, of the 1-propyl1-methylpiperidinium bis{(trifluoromethyl)sulfonyl}imide, [PMPIP][NTf2], with water was presented earlier as immiscible * To whom correspondence should be addressed. Tel.: +48 22 621 3115. Fax: +48 22 628 2741. E-mail:
[email protected]. † Warsaw University of Technology. ‡ University of KwaZulu-Natal.
in the liquid phase system with an upper critical solution temperature, UCST.8 After years of measurements of phase equilibria and of ∞ activity coefficients at infinite dilution, γ13 , we can conclude that the piperidinium-based ILs could be, by the similarity to pyrrolidinium-based ILs, very promising.1,12–16 Recently, the activity coefficients of many organic solvents and water were measured in [PMPIP][NTf2].17 The selectivities obtained for the separation of the aromatic hydrocarbons from the aliphatic hydrocarbons were on the average level, but the selectivity for the heptane/thiophene separation problem was ∞ quite high, S12 ) 29.9 at T ) 323.15 K. The choice of anion in this work is a result of our systematic ∞ measurements of γ13 and phase equilibria for the thiocyanate18–23 based ILs. In separation processes, the selectivity and capacity can be directly calculated from activity coefficients at ∞ infinite dilution (γ13 ) for different separation problems.24 Two thiocyanate-based ILs, 1-ethyl-3-methylimidazolium thiocyanate, [EMIM][SCN], and 1-butyl-3-methylimidazolium thiocyanate, [BMIM][SCN], were investigated by us as separation media for aliphatic and aromatic hydrocarbons and for thiophene and aliphatic hydrocarbons with very high selectivities and average capacities.18,19 The highest selectivity values ever published indicated that these two ILs are the best for solvent extraction processes for different separation problems. It is generally known that an increase of the alkyl chain length increases the capacity and decreases the selectivity for different ILs (imidazolium, pyridinium, pyrrolidinium, and ammonium). The aim of this work was to measure activity coefficients at infinite dilution of the piperidinium-based IL: 1-butyl-1-methylpiperidinium thiocyanate [BMPIP][SCN] in alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, and water using a gas-liquid chromatography (GLC) method. The investigation includes the effect of the alkyl chain length of the solutes and the influence of temperature.
10.1021/je101008y 2011 American Chemical Society Published on Web 12/17/2010
Journal of Chemical & Engineering Data, Vol. 56, No. 1, 2011 125 Table 1. Investigated IL: Chemical Structure, Name, and Abbreviation
Table 2. Column Specification and Chromatograph Condition column 1 loading /% mass coated/g column length/m column i.d. /mm column temperature/K injector temperature/K detector temperature/K carrier gas flow/cm3 · min-1
[BMPIP][SCN]
column 2
44.93 4.4616
35.26 3.8347
1 4 318.15-368.15 423.15 423.15 helium 15-100
Experimental Section Materials and Methods. The IL was as follows: [BMPIP][SCN] (IoLiTec Ionic Liquids Technology GmbH, Germany Merck, Germany, 0.98 in mass fraction; synthesized on request). The structure of the IL is shown in Table 1. All high purity solvents were supplied from Sigma-Aldrich and were used without any further purification because the GLC technique separated any impurities on the colums. The experiments were performed using a PerkinElmer Clarus 500 gas chromatograph equipped with a thermal conductivity detector (TCD). The data were collected and processed using TotalChrom Workstation software. The column preparation and the packing method used in this work have been described previously.25,26 Glass columns of lengths (1 and 4) mm internal diameter were used. Chromosorb W HP 80/100 mesh was used as the solid support and was supplied by SUPELCO. Coating the solid support material with the IL was performed by dispersing a certain portion of Chromosorb in a solution of the IL in methanol followed by evaporation of the solvent using a rotating evaporator. The masses of the stationary phase and of the solid support were weighed with a precision of ( 0.0001 g. The solvent column packing varied from (35.26 to 44.93) mass percent of the IL, large enough to prevent any residual adsorption of solute onto the column packing. For each temperature the measurements were repeated by using two different columns with different mass percent packing (see Table 2). The results of the measurements for two different columns at two temperatures are shown as an example in Table 1S in the Supporting Information (SI). Care was taken to ensure that the methanol had completely evaporated from the IL-coated solid before making up the column. Before the experiment each column was conditioned by blowing carrier gas at a high flow rate (about 2.0 cm3 · s-1) at the high temperature (about 373 K) through about 8 h. The outlet pressure Po was kept at atmospheric pressure. The pressure drop (Pi - Po) was varied between (55 and 80) kPa depending on the flow rate of the carrier gas. The pressure drop was measured by a gas chromatograph with an uncertainty of ( 0.1 kPa. The atmospheric pressure was measured using a digital barometer with an uncertainty of ( 0.01 kPa. The carrier gas was helium. The flow rate of carrier gas was (15 to 100) cm3 · min-1 and determined using a calibrated soap bubble flowmeter which was placed at the outlet after the detector. There was one flow rate for one solute, and the picture of this is shown in Table 2S in the SI. The flow rate was set for
a series of runs and was allowed to stabilize for at least 15 min ∞ before any γ13 determinations were made. The flow rates were corrected for water vapor pressure. Solute injections ranged from (0.01 to 0.3) µL and were considered to be at infinite dilution on the column. Experiments were carried out at different temperatures (in steps of 10 K) between (318.15 and 358.15) K. The temperature of the column was maintained constant to within ( 0.02 K. At a given temperature, each experiment was repeated 2 to 4 times to check the reproducibility. Retention times were generally reproducible within (0.001 to 0.01) min depending on the temperature and the individual solute. At each temperature, values of the dead time tG identical to the retention time of a nonretainable component were measured. While our GC was equipped with a TCD detector, air was used as a nonretainable ∞ was less than 3 component. The estimated overall error in γ13 %, taking into account the possible errors in determining the column loading, the retention times, and solute vapor pressure. The GLC technique was tested for the system hexane in hexadecane at 298.15 K, and the results compared very favorably with the literature values.27
Theoretical Basis The equation developed by Everett28 and Cruickshank et al.29 ∞ was used in this work to calculate the γ13 of solutes in the IL:
( )
ln γ∞13 ) ln
P*(B n3RT PoJ23(2B12 - V∞1 ) 1 11 - V*) 1 + VNP*1 RT RT (1)
The VN denotes the net retention volume of the solute, Po the outlet pressure, PoJ23 the mean column pressure, n3 the number of moles of solvent on the column packing, T the column temperature, P*1 the saturated vapor pressure of the solute at temperature T, B11 the second virial coefficient of pure solute, V*1 the molar volume of the solute, V∞1 the partial molar volume of the solute at infinite dilution in the solvent, and B12 (where 2 refers to the carrier gas, helium), the mixed second virial coefficient of the solute and the carrier gas. The values of B11 and B12 were calculated using the McGlashan and Potter30 equation for alkanes and Tsonopolous31 equation for the rest of solvents. Using the Hudson and McCoubrey combining rules,32,33 critical parameters for mixtures were calculated from the critical properties of the pure component. The pressure correction term J23 is given by 3
J2
3 2 (Pi /Po) - 1 ) 3 (P /P )2 - 1 i o
(2)
The net retention volume of the solute VN, is given by
VN ) J23Uo(tR - tG)
(3)
where tR and tG are the retention times for the solute and an unretained gas, respectively, and Uo is the column outlet flow rate. The vapor pressure values were calculated using equation and constants taken from the literature.34–36 Critical data used to calculate B11 and B12 were obtained from literature.37,38 The fundamental values of critical parameters and B11 and B12 were presented in our previous work in the SI.39
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Table 3. Average Experimental Activity Coefficients at Infinite Dilution γ∞13 for the Solutes in the IL [BMPIP][SCN] at Different Temperatures and Excess Molar Enthalpies at Infinite Dilution, ∆HE,∞ 1 ∆HE,∞ 1
T/K hexane heptane octane nonane decane cyclopentane cyclohexane cycloheptane cyclooctane hex-1-ene hept-1-ene oct-1-ene hex-1-yne hept-1-yne oct-1-yne benzene toluene ethylbenzene o-xylene m-xylene p-xylene methanol ethanol water thiophene THF MTBE diethyl ether dipropyl ether dibutyl ether acetone pentan-2-one pentan-3-one
318.15
328.15
338.15
348.15
358.15 kJ · mol-1
a
104 142 206 293 433 24.4 36.0 41.5 54.1 36.7 55.7 83.0 6.10 9.20 13.6 1.93 3.17 5.18 4.18 5.24 5.04 0.361 0.627 0.331 1.13 2.31 12.7 11.5 32.8 73.4 1.49 3.06 3.07
89.2 127 185 267 390 22.2 32.6 37.4 49.2 34.5 51.9 77.0 6.16 9.21 13.6 1.95 3.19 5.17 4.21 5.25 5.06 0.361 0.616 0.335 1.17 2.34 12.3 11.0 30.9 68.1 1.49 3.06 3.09
78.4 111 161 233 342 20.1 29.6 34.7 44.8 32.1 48.1 71.3 6.19 9.25 13.7 1.98 3.21 5.16 4.24 5.26 5.09 0.361 0.606 0.340 1.20 2.36 12.0 10.7 29.2 63.5 1.49 3.07 3.10
68.5 102 150 214 310 19.1 27.7 32.8 42.2 30.2 45.9 67.2 6.22 9.31 13.7 2.00 3.23 5.15 4.26 5.27 5.12 0.362 0.599 0.345 1.23 2.39 11.7 10.4 27.9 60.5 1.50 3.07 3.10
124 170 236 333 487 27.7b 39.9 44.3 60.0 40.9 60.4 89.6 6.06 9.17 13.6 1.90c 3.14 5.19 4.15 5.23 5.00 0.360 0.639 1.10 2.28 13.1 11.9 35.1 79.2 1.48 3.05 3.07
13.9 12.1 10.9 10.5 10.8 8.9 8.8 7.4 8.5 7.0 6.6 6.9 -0.60 -0.33 -0.21 -1.1 -0.66 0.17 -0.60 -0.17 -0.53 -0.13 1.6 -1.4 -2.5 -1.1 2.6 3.3 5.4 6.5 -0.23 -0.17 -0.30
Figure 1. Plot of ln(γ∞13) versus 1/T of [BMPIP][SCN] with solutes: b, hexane; 2, heptane; 9, octane; +, nonane; ×, decane; ), cyclopentane; O, cyclohexane; 4, cycloheptane; 0, cyclooctane.
a The error is 124 ( 3.7. b The error is 27.7 ( 0.8. c The error is 1.90 ( 0.06.
Results and Discussion ∞ The average γ13 values are listed in Table 3. The values of for homological series of solutes increase with an increase of the solute alkyl chain length. This is typical dependence, observed for all ILs. The smallest interaction with solutes and the highest values of γ∞13 were observed for alkanes (for example ∞ ) 170 at T ) 318.15 K), cycloalkanes, and for heptane γ13 alkenes. Much lower values for the same carbon number were obtained for alkynes. The dibutyl ether has a surprising high ∞ ) 79.3 at T ) 318.15 K). The cyclic structure of value (γ13 ∞ in comparison to the cycloalkanes reduces the value of γ13 ∞ corresponding linear alkane. The γ13 is in the same range of order for hex-1-ene and for cyclohexane, but for longer chain alkenes these values are much higher for the cyclohydrocarbons with the same carbon number. Alkynes and aromatic hydro∞ than alkanes, cycloalkanes, carbons have smaller values of γ13 and alkenes. For benzene and thiophene the values are 1.90 and 1.10, respectively (T ) 318.15 K), which is lower than for ethers and ketones. The smallest values of γ∞13, indicating the strongest interactions between solvent and solute, was observed for water. ∞ are slightly higher than those for For alcohols the values of γ13 water. These polar compounds usually interact very strongly with a polar IL. In this case, the major influence on values of γ∞13 has very strong interactions between -OH group in alcohols with the anion of the IL. Figures 1 to 5 show the natural logarithm of the activity coefficients in the IL as a function of the inverse absolute temperature for all investigated solutes in [BMPIP][SCN]. The ∞ is different for the different temperature dependence of γ13
Figure 2. Plot of ln(γ∞13) versus 1/T for [BMPIP][SCN] with solutes: b, hex-1-ene; 2, hept-1-ene; 9, oct-1-ene; O, hex-1-yne; 4, hept-1-yne; 0, oct-1-yne.
∞ γ13
Figure 3. Plot of ln(γ∞13) versus 1/T for [BMPIP][SCN] with solutes: b, benzene; 2, toluene; 9, ethylbenzene; O, o-xylene; 4, m-xylene; 0, p-xylene.
solutes. The influence of temperature is also typical; with an ∞ increase in temperature the values of γ13 decrease with the exception of alkynes, aromatic hydrocarbons, alcohols (except ethanol), water, tetrahydrofuran (THF), and ketones. Table 3 lists the partial molar excess enthalpies at infinite dilution ∆HE,∞ 1 determined from the Gibbs-Helmholtz equation over the temperature range (318.15 to 358.15) K:
Journal of Chemical & Engineering Data, Vol. 56, No. 1, 2011 127
partial molar excess enthalpies at infinite dilution mean that the interactions between solute and solvent are higher than for similar molecules. For alkynes it is caused by interaction between the triple bond and polar anions of the IL. For THF and ketones, the ∆H1E,∞ values are negative for many different ILs. A very important factor in the design of extraction processes ∞ and capacity k2∞ of is the knowledge about selectivity S12 entrainers, which can be calculated directly from experimental ∞ values: γ13
Figure 4. Plot of ln(γ∞13) versus 1/T for [BMPIP][SCN] with solutes: O, methanol; 4, ethanol; (, water.
S∞12 ) γ∞13 /γ∞23
(5)
k∞2 ) 1/γ∞23
(6)
where “3” is an IL. Table 4 shows influence of structure of ILs based on [BMsubstituted]+ cation or [SCN]- anion on S∞12 and k∞2 for heptane/ benzene, cyclohexane/benzene, and heptane/thiophene separation problems at T ) 323.15 K. The IL investigated in this work, [BMPIP][SCN], reveals the third high value of selectivity after [EMIM][SCN] and [BMIM][SCN].18,19 The selectivity is 81.1 for heptane/benzene, 19.9 for cyclohexane/benzene, and 138.5 for heptane/thiophene. Unfortunately, the capacities were higher for the ILs with the [NTf2]- anion. Many ILs based on butyl-methyl substituents exhibit lower selectivities than [EMIM][SCN], [BMIM][SCN], and [PMPIP][SCN].40–50 For ILs based on the [SCN]- anion, the selectivities are usually much higher than for other ILs, for example, [BMPy][BF4].47
Conclusions Figure 5. Plot of ln(γ∞13) versus 1/T for [BMPIP][SCN] with solutes: b, diethyl ether; 2, dipropyl ether, 9, dibutyl ether; (, THF; ×, methyl tertbutyl ether (MTBE); O, pentan-2-one; 4, pentan-3-one; ), propan-2-one; /, thiophene.
∂ ln γi∞ ∆HE,∞ 1 ) ∂(1/T) R
(4)
The ∆H1E,∞ values are negative for alkynes, aromatic hydrocarbons including thiophene (with exception of ethylbenzene), methanol, water, THF, and ketones. The negative values of the
Activity coefficients at infinite dilution for various solutes in the IL 1-butyl-1-methylpiperidinium thiocyanate were measured, and the high selectivities at infinite dilution for three tested separation problems, heptane/benzene, cyclohexane/benzene, and heptane/thiophene, were found in comparison to similar ILs with different anions. However, the selectivities were lower than those for the imidazolium-based thiocyanate ILs. Supporting Information Available: Table 1S: the experimental activity coefficients at infinite dilution ∞ γ13 for the solutes in ionic liquid [BMPIP][SCN] at different
Table 4. Selectivities, S∞12, and Capacities, k∞12, at Infinite Dilution for Several ILs Based on the 1-Alkyl-1-methylpyrrolidinium Cation or Thiocyanate Anion, NMP, and Sulfolane for Different Separation Problems at T ) 323.15 K S∞12
k∞2
k∞2
solvent
heptane/benzene
cyclohexane/benzene
heptane/thiophene
benzene
thiophene
ref
[BMPIP][SCN] [PMPIP][NTf2] [EMIM][SCN] [BMIM][SCN] [HMIM][SCN] [BMPy][SCN] [BMPYR][SCN] [BMIM][BF4] [BMIM][CF3SO3] [BMIM][C2H5SO4] [BMIM][MDEGSO4] [BMIM][NTf2] [BMIM][OcSO4] [BMIM][PF6] [BMPy][BF4] [BMPy][NTf2] [BMPy][TOS] [BMPYR][CF3SO3] [BMPYR][NTf2]
81.1 26.2 109 90.7 35.0 66.4 73.0 47.0 28.7 59.8 37.3 20.2 6.1 31.6 49.8 23.5 13.8 38.6 20.8
19.9 11.5 25.7 20.4 11.7 16.1 18.4 15.6 10.6 16.5 12.5 8.6 3.5 10.9 16.3 10.4 5.1 13.9 9.0
138.5 29.9 156 53.0 112 123 39.3 42.0 26.6 53.1 -
0.52 1.07 0.29 0.46 0.50 0.59 0.53 0.41 0.63 0.36 0.50 1.11 0.69 0.51 0.61 1.38 0.25 0.68 1.14
0.89 1.22 0.79 0.76 0.99 0.93
this work 17 18 19 20 40 40 41 42 43 44 43 45 46 47 48 49 12 50
0.86
0.68 1.56 0.94
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temperatures for two columns; table 2S: the flow rates for different solutes. This material is available free of charge via the Internet at http://pubs.acs.org.
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4-methyl-N-butyl-pyridinium Bis(trifluoromethylsulfonyl)-imide. J. Chem. Thermodyn. 2009, 41, 1350–1355. (49) Letcher, T. M.; Ramjugernath, D.; Kro´likowski, M.; Laskowska, M.; Naidoo, P.; Doman´ska, U. Activity Coefficients at Infinite Dilution Measurements for Organic Solutes in the Ionic Liquid N-butyl-4-methylpyridinium Tosylate Using GLC at T ) (328.15, 333.15, 338.15, and 343.15) K. Fluid Phase Equilib. 2009, 276, 31–36. (50) Kato, R.; Gmehling, J. Systems With Ionic Liquids: Measurement of VLE and C1 Data and Prediction of Their Thermodynamic Behavior Using Original UNIFAC, mod. UNIFAC(Do) and COSMO-RS(Ol). J. Chem. Thermodyn. 2005, 37, 603–619. Received for review October 7, 2010. Accepted December 1, 2010. This work has been supported by the European Union in the framework of European Social Fund through the Warsaw University of Technology Development Programme.
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